Petroleum hydrocarbon ecological risk and changes induced on macrobenthic communities of a microtidal estuary in South America.

The coastal areas of Montevideo-Canelones, Uruguay, are strongly affected by anthropogenic activities. Polycyclic aromatic hydrocarbons (PAHs) are of especial ecological concern due to their acute toxicity. The study aimed to evaluate the relationship between different pollution levels and the ecological structure of macrobenthic communities of the subtidal coastal zone and to assess the ecological risk of the 16 PAHs identified by US EPA for these communities. Communities in Montevideo Bay are under the influence of combined effects of natural oscillations and anthropic pollution, while the adjacent coastal areas communities are strongly influenced by El Niño Southern Oscillation. Toxicity assessments classified two sites in Montevideo Bay as medium to low risk. This study allowed recognizing the complex nature of the responses of benthic organisms to multiple stressors and the importance of considering different approaches.

Biochemical responses in Pacific oysters Magallana gigas (Thunberg, 1793): Tools to evaluate the environmental quality of aquaculture areas.

The discharge of sanitary sewage into the bays of the Florianópolis Metropolitan Area (Southern Brazil), has led to the contamination of oyster farms. Consequently, linear alkylbenzenes (LABs) were quantified in the sediment, and the biochemical responses in gills and digestive gland of oysters from six farms were assessed. Our findings revealed elevated levels of LABs in the sediment of the Imaruim and Serraria farms. Additionally, alterations were observed in the antioxidant enzymes: catalase, glutathione peroxidase and superoxide dismutase in both oyster tissue from the Serraria, Santo Antonio de Lisboa and Sambaqui farms. Furthermore, correlation analyses indicated strong and moderate associations between biochemical responses, organic contaminants, and certain physicochemical parameters. Consequently, our results demonstrated the activation of the antioxidant system in oysters, representing a protective response to the presence of sanitary sewage and other contaminants. Therefore, we propose the utilization of biochemical biomarkers for monitoring the environmental quality of farms.

Persistent organic pollutants and polycyclic aromatic hydrocarbons in livers of stranded Arctocephalus australis in southern Brazilian beaches.

23 livers of South American fur seal (Arctocephalus australis) found stranded in southern Brazilian beaches were evaluated for Persistent Organic Pollutants (POPs) and Polycyclic Aromatic Hydrocarbons (PAHs). POPs (DDTs, mirex, eldrin, dieldrin, aldrin, isodrin, HCHs, chlordanes and PCBs) and PAHs in livers were Soxhlet extracted, analyzed and quantified using Gas Chromatography Tandem Mass Spectrometry (GC-TQMS). The main POPs found were PCBs and DDTs, totaling 81 %. Among pesticides, mirex followed DDTs, possibly due to usage in Uruguay, followed by Σdrins, ΣCHLs and ΣHCHs. Naphthalene was the major PAH found, while heavier compounds did not significantly bioaccumulate. Concentrations of POPs resembled previous findings for A. australis. Considering only juveniles, no POPs showed significant differences between sexes. Lipidic content, weight and length did not show any correlation with POP concentration. This was the first record of PAHs and PBDEs in South American fur seals, and the levels of these pollutants were relatively low.

Mobilization of persistent organic pollutants in humpback whales: Insights from feeding areas in the Antarctic peninsula and Strait of Magellan to migration, breeding, and calving grounds along the Brazilian coast.

Southern Hemisphere Megaptera novaeangliae undertake the longest migration, which reflect their exposure to lipophilic contaminants. To assess these changes, persistent organic pollutants were analyzed in blubber samples of humpback whales from three regions: the Antarctic Peninsula (n = 46), the Strait of Magellan, Chile (n = 22), and the Brazilian coast (n = 38). The similarity in PCB and HCB levels between individuals from feeding grounds and breeding grounds suggests contamination during feeding. The whales around the Antarctic Peninsula exhibited a predominance of tetrachlorobiphenyl PCBs. Whales feeding in the Strait of Magellan showed a slight prevalence of 5Cl biphenyls, likely due to their consumption of subantarctic krill species as well as small fishes potentially contaminated by industrial activities in Chile. The dominance of 5-6Cl congeners in whales in Brazil, may be attributed to the extreme physiological changes during fasting when whales utilize blubber reserves and metabolize lighter congeners, or transfer them to their calves.

Trophic Chain Organochlorine Pesticide Contamination in a Highly Productive Upwelling Area in Southeastern Brazil.

Organochlorine pesticides (OCP) are legacy anthropogenic compounds known to persist for several years in the environment. The continuous use of some OCP, such as DDT, after restrictions in developing countries are cause of concern, due to their deleterious effects to marine life and humans. Studies assessing OCP contamination in coastal environments are still scarce in South America and there is a need to understand the impacts from trophic chain accumulation of these pollutants in marine life. In this study, we have assessed OCP levels in muscle and liver and estimated the biomagnification factor in several upwelling system trophic chain members, including fish, squid, and marine mammal from Southeastern Brazil. DDT degradation product DDE was the OCP detected in the highest concentrations in Franciscana dolphins (Pontoporia blainvillei), 86.4 ng·g-1 wet weight, and fish muscle and liver. In general, higher OCP levels were found in liver than in muscle, except for croaker. Biomagnification factors (BMF) of OCP in the top predator P. blainvillei and the carnivorous cutlass fish (Trichiurus lepturus) were on average between 0.2 and 1.8. Continued OCP monitoring in this region is warranted to better understand the distribution and fate of these compounds over time, with the goal to establish strategies for the conservation of local dolphin species and to assess human health risks from local coastal region populations.

Comparative biochemical and molecular responses of biotransformation and antioxidant systems in three species of Crassostrea (Sacco, 1897) oysters exposed to chrysene.

Chrysene (CHR) is among the most persistent polycyclic aromatic hydrocarbons (PAH) in water and a priority compound for pollutants monitoring, due to its carcinogenic, mutagenic and genotoxic potential. Aquatic animals exposed to CHR may present alterations of biomarkers involved in the biotransformation and oxidative stress-related parameters. The aim of this study was to investigate differences in antioxidant and biotransformation (phase I and II) systems of Crassostrea gigas, C. gasar and C. rhizophorae and its effects resulting from CHR exposure. Adult oysters of these species were exposed to 10 µg L-1 of CHR for 24 h and 96 h. In gills, the transcripts CYP1-like, CYP2-like, CYP2AU1-like, GSTO-like, MGST-like, SULT-like were evaluated after 24 h of exposure. The activity of SOD, CAT, GPx, GR and G6PDH were analyzed in gills and digestive glands after 96 h of exposure. CHR bioaccumulated in tissues. Differences in the remaining levels of CHR in water after 96 h were observed in aquaria containing C. gigas or C. gasar oysters and may be associated to the different filtration rates between these species. Downregulate of biotransformation genes were observed in gills of C. gasar (CYP2AU1-like and GSTO-like) and C. rhizophorae (CYP1-like1, CYP2-like, MGST-like and SULT-like), suggesting that biotransformation responses may be species-specific. Differential activity of antioxidant enzymes were observed in gills and digestive gland of oysters exposed to CHR. Biochemical responses suggested that C. gigas and C. gasar are more responsive to CHR. Differential responses observed among the three Crassostrea species can be related to evolutionary differences, ecological niches and adaptation to environment.

Persistent organic pollutant patterns in seabirds from marine protected areas in the tropical Atlantic Ocean.

Persistent organic pollutants were investigated in the blood of living seabirds (Pterodroma arminjoniana, Onychoprion fuscatus, Sula dactylatra, Anous minutus, Anous stolidus and Sula leucogaster) from two Brazilian Conservation Units - Trindade Island and São Pedro and São Paulo Archipelago. ∑PCBs (0.55 to 55.09 ng/g wet weight (ww), ∑DDTs (0.01 to 17.36 ng/g ww) and Mirex (0.01 to 5.53 ng/g ww) were predominant in all samples. Trindade petrel Pterodroma arminjoniana presented higher values than other seabirds, which is potentially related to diet and migratory behavior. Fluctuations in the trophic ecology data, through carbon and nitrogen stable isotope ratios, warn of temporal variation in diet and foraging and highlight the importance of using a nondestructive matrix to allow long-term monitoring of POP contamination in seabirds from Brazilian Conservation Units. In addition, the data will fill the gaps in the POP baselines for seabirds from the tropical Atlantic Ocean.

Gender influences molecular and histological biomarkers in mature oysters Crassostrea gasar (Adanson, 1757) after pyrene exposure.

Oysters are frequently used as sentinel organisms for monitoring effects of contaminants due to their sessile, filtering habits and bioaccumulation capacity. These animals can show elevated body burden of contaminants, such as pyrene (PYR). PYR can be toxic at a molecular level until the whole oyster, which can show reproductive and behavioral changes. Considering that biologic parameters, such as gender or reproductive stage can interfere in the toxic effects elicited by contaminants uptake, the aim of this study was to evaluate some molecular and histological responses in females and males of oyster Crassostrea gasar exposed to PYR (0.25 and 0.5 µM) for 24 h at the pre-spawning stage. PYR concentrations were analyzed in water and in tissues of female and male oysters. Gene transcripts related to biotransformation (CYP3475C, CYP2-like, CYP2AU1, CYP356A, GSTO-like, GSTM-like, SULT-like), stress (HSP70), and reproduction (Vitellogenin, Glycoprotein) were quantified in gills. In addition, histological analysis and histo-localization of CYP2AU1 mRNA transcripts in gills, mantle and digestive diverticulum were carried out. Females and males in pre-spawning stage bioconcentrated PYR in their tissues. Males were more sensitive to PYR exposure. CYP2AU1 transcripts were higher in males (p < 0.05), as well as tubular atrophy was observed only in males exposed to PYR (p < 0.05). As expected, vitellogenin transcripts were lower in males (p < 0.05). Given these results, it is suggested that levels of CYP2AU1 be a good biomarker of exposure to PYR in oyster C. gasar and that it is important to consider the gender for the interpretation of biomarker responses.

Temporal trends of persistent organic pollutant contamination in Franciscana dolphins from the Southwestern Atlantic.

Persistent organic pollutants (POPs) were analyzed in 136 blubber samples of Franciscana dolphins from Brazil (Pontoporia blainvillei), which is the most threatened dolphin in the Southwestern Atlantic. The dolphins were caught by the fishery fleet and collected from 2000 to 2018 in three regions of São Paulo state: northern São Paulo (SPN), central São Paulo (SPC), and southern São Paulo (SPS). The POPs analyzed in this study were polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDTs), Mirex, hexachlorobenzene (HCB), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs), and polybrominated diphenyl ethers (PBDEs). The concentrations ranged from 36 to 7200 ng g-1 lipid weight (lw) and 113-42200 ng g-1 lw for predominant compounds DDTs and PCBs, respectively. Similar profiles of PCB congeners were observed with a predominance of hexachlorinated compounds, representing approximately 50% of the total PCB amount; the highest PCB concentrations were observed from Baixada Santista (SPC) proximate to a highly urbanized and industrial coastal area. Significant differences were observed between the sexes and maturity of dolphins, mainly for PCBs, DDTs, and Mirex. In general, POPs other than HCB in Franciscana dolphins showed downward temporal trends, matching the regulatory periods for restricting and/or banning these compounds. Although POP concentrations are declining, PCB levels remain high in small dolphins, suggesting adverse health effects on Franciscanas. As organic contaminants are one of the numerous threats Franciscanas have been vulnerable to along the Brazilian coast, we recommend monitoring POPs levels every five years to check for declining (or stabilizing) trends.

Microplastics and linear alkylbenzene levels in oysters Crassostrea gigas driven by sewage contamination at an important aquaculture area of Brazil.

The levels of linear alkylbenzenes (LABs) and the occurrence of microplastics (MPs) in the oysters Crassostrea gigas were evaluated in six farming areas in southern Brazil. The results revealed higher concentrations of LABs in oyster tissue from the Serraria (1977 ± 497.7 ng g-1) and Imaruim (1038 ± 409.9 ng g-1) sites. Plastic microfibers were found in oysters from all locations with values from 0.33 to 0.75 MPs per oyster (0.27-0.64 MPs per gram) showing the ubiquitous presence of this contaminant in the marine environment, which could be considered a threat to farming organisms. In addition, elements such as Ti, Al, Ba, V, Rb, Cr, and Cu were found in the chemical composition of the microfibers, suggesting MPs as vectors of inorganic compounds. A positive correlation between LABs and thermotolerant coliforms suggests that sewage discharges are the main source of contamination in these oysters cultured for human consumption. The present study highlights the need for efficient wastewater treatment plants and the implementation of depuration techniques in oysters from farming areas.

Unusual natural polycyclic aromatic hydrocarbons in sediment cores of an Amazon estuary.

Polycyclic aromatic hydrocarbons (PAHs) most likely derived from natural sources were observed in two sediment cores covering the last 100 years in an Amazon estuarine region. A considerable change in the PAHs main source was observed in the 1960s. Before the 1960s, the sources of PAHs seem to be related to biogenic and/or early-diagenetic processes. Concentrations of perylene were higher before the 1960s and suggest that its primary source to the sediments in the Amazon region is linked to a short-term diagenetic transformation of their biogenic precursors. The natural formation of alkylated PAHs in sediments was linked to the methylation of the parental aromatic hydrocarbons due to sediment maturation processes and the dehydrogenation of sterols in the sediments. The relatively rapid reaction occurring in recent sediments of the Amazon region suggests the importance of the microbial community in the transformation of biogenic precursors to alkylated-PAHs in the sediments.

Molecular changes in oysters Crassostrea gigas (Thunberg, 1793) from aquaculture areas of Santa Catarina Island bays (Florianópolis, Brazil) reveal anthropogenic effects.

Anthropogenic activities in coastal regions cause risks to the environmental and human health. Due to the carcinogenic and mutagenic potential, polycyclic aromatic hydrocarbons (PAH) are considered priority for monitoring. Most of the Brazilian production of Crassostrea gigas oysters are placed in the Bays of Santa Catarina Island. The aim of this study was to evaluate molecular responses (phase I and II of biotransformation and antioxidant defense) of C. gigas from six oyster farming areas potentially contaminated by sanitary sewage in Florianópolis Metropolitan (SC, Brazil): Santo Antônio de Lisboa, Sambaqui, Serraria, Caieira, Tapera, Imaruim. We evaluated the transcript levels of CYP1A1-like, CYP2-like, CYP2AU2-like, CYP356A1, GSTA1A-like, GSTO.4A-like, SULT-like, SOD-like and CAT-like by qRT-PCR. Only oysters from Caieira showed levels of thermotolerant coliforms allowed by the law. Chemicals analyses in soft tissues of oysters showed low to average levels of PAH in all monitored areas. Enhanced transcript levels of phase I (CYP1A1-like, CYP3564A1-like, CYP2-like and CYP2AU2-like) were observed in oysters from Serraria and Imaruí, suggesting higher biotransformation activity in these farming areas. Regarding phase II of biotransformation, GSTO.4A-like was up-regulated in oysters from Imaruí compared to Caieira and Santo Antônio de Lisboa. An upregulation of SOD-like and CAT-like were observed in oysters from Imaruí and Serraria, suggesting that oysters from these sites are facing higher prooxidant conditions compared to other areas. By integrating the biological and chemical data it is suggested that human-derived contaminants are affecting the oyster metabolism in some farming areas.

Mollusc shell shape as pollution biomarkers: Which is the best biological model?

Alterations in mollusc shells have been proposed contamination biomarkers. We used geometric morphometrics analyses associated with analytical determinations of contaminants to select suitable biological models among species widely distributed on coastal zones. The study was carried out using Lottia subrugosa (herbivore limpet), Crassostrea brasiliana (filter-feeder bivalve), and Stramonita brasiliensis (carnivore gastropod) obtained along a marked contamination gradient at Santos Estuarine System (Brazil). L. subrugosa and S. brasiliensis presented distinct shapes along the gradient, while no significant differences in shell form were seen for C. brasiliana. Indeed, limpets and snails presented morphometric parameters consistent with measured contamination levels hazardous substances. Based on cross-validation models, the reliability of morphometric responses was over 75% for the herbivore and carnivore species. In addition, for S. brasiliensis, a 95.2% confidence was detected in most contaminated sites. Therefore, shell alterations on carnivorous gastropods should be further investigated, seeking to be effectively employed as pollution biomarkers.

Persistent organic pollutants and stable isotopes in the liver of Chelonia mydas stranded on the southeastern Brazilian coast.

Among the various pollutants released into the environment, there are persistent organic pollutants (POPs). Chelonia mydas are one of the species that can be exposed to these pollutants and it is classified in the IUCN Red List as "endangered". The present study evaluated the occurrence of POPs in 49liver tissue samples of C. mydas juveniles collected on the southeastern Brazilian coast. Furthermore, the concentrations were correlated with carbon and nitrogen isotopic ratio, biometrics, and ecological factors. The main POPs found were Æ´-HCH and PCBs. Overall, the concentrations found were low and there were no significant correlations among POPs, isotopic ratios, size and weight, which may be related to the fact that the studied individuals are juveniles and occupy similar trophic positions despite the individual variations found. Despite the low concentrations, the presence of POPs, mainly PCBs, in the sea turtles' liver indicates their exposure to these compounds.

Organic contaminants in marine environment - Let us not forget the shallow areas.

The evaluation of anthropogenic pressures in marine environments commonly involves sediments, water and marine biota. However, the evaluation of the quality of the beach sediment and sediments from shallow areas are scarce compared to sediments from deeper areas in environmental assessment studies. In this study polycyclic aromatic hydrocarbons and linear alkylbenzenes were assessed in sediments from shallow areas of the São Sebastião channel, southeastern Brazil. The channel is part of the Marine Protected Area of the Northern Coast of São Paulo State besides holds the largest petroleum terminal in South America further than three sewage outfalls. Despite the concentrations of these contaminants in the sediments were relatively low compared to those found in the sediments from deeper areas of the channel, suggesting low toxicity of the beach sediments, the contamination reflected the pattern of the sediments of the São Sebastião channel.

Historical deposition of PAHs in mud depocenters from the Southwestern Atlantic continental shelf: The influence of socio-economic development and coal consumption in the last century.

Polycyclic aromatic hydrocarbon (PAH) concentrations were determined in four dated sediment cores collected in mud depocenters of the southern Brazilian continental shelf. Core dating results covered the interval between 1925 and 2017. The total PAH concentrations (ΣPAHs) ranged from 44.69 ng g-1 to 305.43 ng g-1 and were similar between the analysed cores. Fine-grained sediments and total organic carbon (TOC) results did not correlate with the ΣPAHs, indicating that the variations in PAH concentrations are mostly related to variations in sources and emissions. PAH source appointment indicated a high input of a natural compound (perylene) and the predominance of anthropogenic PAHs from coal, biomass, and fuel combustion. Alkylated PAHs presented high contributions throughout all cores. The historical deposition of PAHs was associated with different periods of the socio-economic and industrial development of near coastal cities and reflected very well the history of coal production and consumption in the southern region of Brazil. The low levels of ΣPAHs before 1945 in all analysed cores may be related to the beginning of the industrialization process and the lower urbanization degree in the region. Between 1945 and 1965, the gradual ΣPAHs increase reflects the establishment and enlargement of the southern Brazilian industrial sector. The interval between 1965 and 1990 corresponded to the highest ΣPAHs in three of the four analysed cores. After 1990, a relative decrease in the ΣPAHs was observed in most cores and may be related the multiple cuts of incentives to the industrial usage of coal, as well as to Brazil's efforts in environmental regulation for coal extraction and consumption.

Persistent organic pollutants in plasma and stable isotopes in red blood cells of Caretta caretta, Chelonia mydas and Lepidochelys olivacea sea turtles that nest in Brazil.

Studies of persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), organochlorinated pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs), in sea turtles are reported, but there are still spatial data gaps worldwide. POP contamination of live female blood plasma from Caretta caretta (n = 28), Chelonia mydas (n = 31) and Lepidochelys olivacea (n = 19), which nest in Brazil and feed along the South Atlantic Ocean, was investigated. Carbon and nitrogen stable isotopes from red blood cells (RBC) were also evaluated to obtain information about trophic ecology. C. caretta had the highest POP concentrations, followed by L. olivacea and C. mydas. PCBs predominated in all species, and the major OCPs were the DDTs (dichlorodiphenyltrichloroethane and derivatives) and Lindane. POPs and stable isotopes revealed intra- and interspecific variations, which reflect the high plasticity in the use of habitat and food resources, making individuals within the same population susceptible to different exposures to pollutants.

Can the environmental health of urban centers be assessed through pollutants trapped in lakes? A study case in the biggest city of the southern hemisphere.

Air and water quality in urban centers are summited to pollution from different sources, such as industrial activities, traffic, and wastewater effluents. A great number of chemicals can be spread by wind throughout the city, exposing the inhabitants to the health risks associated to them. Atmospheric analysis provides punctual data and represents the timing of the air sampling. A long-term evaluation of the atmospheric air quality can be assessed through the evaluation of pollutants that reach the soil by atmospheric deposition; however, they also can be redistributed and desorbed. The evaluation of pollutants in lakes could be a practical solution, given that lakes may act as traps to these compounds. In this context, organic pollutants were assessed in sediment and water from a lake located in the urban area of São Paulo, Brazil, the biggest city of the southern hemisphere. There were no evidences of sewage input to the lake and pyrogenic compounds reached the lake through atmospheric deposition. The content of pyrogenic PAH exposed the large amount of PAH emitted to the atmosphere by the multiple sources of PAH, mainly vehicular emission and diesel combustion. The PAH trapped in the lake highlighted the impact of all burning process in the air quality in which 12.3 million people are exposed.

Integrated biomarker responses in oysters Crassostrea gasar as an approach for assessing aquatic pollution of a Brazilian estuary.

The Laguna Estuarine System (LES), southern Brazil, suffers impacts from anthropogenic activities, releasing contaminants into the ecosystem. This study evaluated changes in biochemical and molecular biomarkers and contaminants concentrations in oysters Crassostrea gasar transplanted and kept for 1.5 and 7 days at three potentially contaminated sites (S1, S2, and S3) at LES. Metals varied spatiotemporally; S1 exhibited higher Ag and Pb concentrations, whereas Cd was present in S3. S2 was a transition site, impacted by Ag, Pb, or Cd, depending on the period. Organic contaminants concentrations were higher before transplantation, resulting in the downregulation of biotransformation genes transcripts levels. Phase II-related genes transcripts and metals showed positive correlations. Decreased levels of HSP90-like transcripts and antioxidant enzymes activity were related to increased pollutant loads. Integrated biomarker response index (IBR) analysis showed S1 and S3 as the most impacted sites after 1.5 and 7 days, respectively. Regardless of the scenario, LES contaminants pose a significant threat to aquatic biota.

Anthropogenic and natural inputs of polycyclic aromatic hydrocarbons in the sediment of three coastal systems of the Brazilian Amazon.

Polycyclic aromatic hydrocarbons (PAHs) were measured in 32 surface sediment samples collected around three cities (Barcarena, Belém, and Santana) located on the coast of the Brazilian Amazon. The concentration of total PAHs ranged from lower than detection limit to 33,101 ng g-1 in a sample from Barcarena and was related to a large aluminum industrial complex and port activities. In Belém, which is the most populated area in the Amazon region, PAHs were probably derived from untreated sewage discharge and inputs from a large municipal landfill. Pyrogenic PAHs were predominant in both cities, with a smaller contribution of petrogenic PAHs. Low alkylated PAH levels may be associated with small boats and ship traffic. Santana had low total PAH concentrations, with a predominance of unusual alkylated PAHs, probably related to diagenetic transformations of organic matter in the sediment. In general, PAH concentrations in the samples were low and may reflect baseline levels for this Amazon estuarine system.